Stable olefin catalyst systems



United States Patent Ofiice savanna STABLE GLENN CATALYST SYSTEMS ArthurK. lngherrnan, Somerville, N.J., assignor to Union Carbide Corporation,a corporation of New York No Drawing. Filed Aug. 21, 1961, Ser. No.132,578 21 Claims. ((Il. 252-429) This invention relates toorgano-metallic olefin catalyst systems characterized by exceptionalretention of catalytic properties and method for preparing suchcatalysts. The invention further relates to the production of polymersof olefinically unsaturated hydrocarbons by the low pressure processemploying novel, highly stable organo-metallic olefin catalysts systems.

K. Ziegler has described the preparation of high molecular Weightpolymers of olefinically unsaturated hydrocarbons by contacting themonomer with a mixture of an organo-aluminum compound and a compound ofa metal of groups lVb, Vb or Vlb of the periodic table.

These catalysts have heretofore been produced by the reaction in aninert solvent medium of the organo-aluminum compound and the metalhalide to form an insoluble complex as a precipitate, which is thecatalyst. This precipitate is ordinarily in a finely divided condition.

These finely divided catalysts are characteristically sensitive toatmospheric contamination. In addition they appear to be inherentlyunstable. A typical catalyst is a hydrocarbon insoluble complex oftitanium tetrachloride and triisobutyl aluminum prepared in an heptanemedium. The rapid decline in catalytic activity of this typical Zieglercatalyst has been documented recently by A. Orzechowski, l. Polymer Sci.34, 745 (1959). The

data appearing in Table 1 following on yield of polyethylene afterperiods of aging in an inert atmosphere is taken from the Orzechowskiarticle. The gram polymer/gram catalyst data are calculated from theOrzechowski data. Aging in each instance is the elapsed time betweenplacing of the catalyst in the polymerization vessel and introduction ofethylene into the vessel.

it can be seen from Table I that after only 1 to 2 minutes 40% of theoriginal catalyst activity had been lost, after 15 minutes 84% had beenlost and after 30 minutes 98 to 99% had been lost. These data reflectthe inherent instability of conventionally prepared transition metalhalide alkyl aluminum catalyst complexes in even inert atmospheres.

As a result of this poor stability these catalysts have heretofore hadto be freshly prepared for each polymerization which of course isinconvenient and costly. Consequences of using partially inactivatedcatalyst include low yields of polymer and undesirably highconcentrations of catalyst residue in the polymer obtained.

It is an object, therefore, of the present invention to providetransition metal halide-alkyl aluminum catalyst systems which aresubstantially unaffected in catalytic activity by aging for extendedperiods, even at elevated temperatures.

it is another object to provide a method for the preparation oftransition metal halide-alkyl aluminum catalyst systems which aresubstantially unaffected in catalytic Patented Apr. 20, 1965 2 activityby aging for extended periods and at elevated temperatures.

It is a further object to provide a process for the production ofpolymers of olefinically unsaturated hydrocarbons wherein highpolymerization rates and minimalcatalyst residues are achieved.

It is still another object to achieve finely divided organometalliccatalysts without grinding.

It has now been discovered that finely divided organometallic catalystsexhibiting high initial activity and resistance to deterioration byaging are prepared by reacting together, under continual high speedagitation providing heat-producing fluid shear, a fluid transition metalhalide and a fluid organo-aluminum compound to PIO-. duce an inert.liquid hydrocarbon insoluble precipitate.

The organo-metallic polymerization catalysts produced by the method ofthis invention are super-finely divided precipitates consisting ofhighly geometrically uniform, essentially spheroidal particles.Precipitates obtained under the hereinafter set. forth preferredconditions of shear producing agitation have an average particle sizediameter between 200 and 300 angstroms with no appreciable number ofparticles greater than 500 angstroms in diameter. The geometry of theparticles produced herein is unlike crushed or ground organo-metalliccomplex precipitates heretofore known which are sharp edged andirregular. The particles obtained are rounded and essentially uniformand are, therefore, not prone to agglomeration. These particles have notbeen obtained heretofore by any method.

A. Ziegler catalyst precipitate prepared in the manner of this inventionsurprisingly retains catalytic properties for many days, Weeks or monthsrather than for only a few minutes as with the same catalysts onlyconventionally prepared. Mere stirring. type agitation or no. agitationat all, such as vides Ziegler catalysts inferior in activity, bothinitially and after aging, to those of this invention. For example, thecatalytic life of a typical Ziegler catalyst, a reaction product oftitanium tetrachloride and triisobutyl aluminum is greatly multiplied byuse of the method of this invention. As shown in Table I above, afteronly 30 minutes of aging at 50 C. the catalyst was reduced onehundredfold in productivity from 240 to 2.3 grams polymer/ gramcatalyst. In contrast to this, a catalyst prepared from these reactantsunder the shear agitation of this invention had a productivity after 20days of room temperature aging, /3 of a month at 25 C.) and then beingheated at C. in an inert atmosphere for 30 minutes, of over 300 grams ofpolymer per gram catalyst. In comparison, a catalyst prepared from thesecomponents by Orzechowski had a maximum productivity of only 240 gramsof polymer per gram of catalyst without any aging and this productivitydeclined a hundred-fold in 30 minutes.

The agitation during reaction necessary to the practice of the method ofthis invention can be achieved with numerous combinations of vessels andagitatiru means known to the art. High speed impellers and rotatingvented cones are preferred types of agitating means. Any apparatuscapable of producing fluid shear suiiicient to give a heat output of atleast 10 calories per minute per liter of agitated fluid in the reactionsystem is suitable Preferred apparatus will accomplish the requisitecalorie output more rapidly by providing a higher speed fluid shear inthe system. This agitation is basically and simply a fluid shear. Shearis present in all agitated vessels to some degree, for example instirred reactors although the reaction mass rotates with the agitatingmeans, some shearing occurs at the interface of the vessel Wall and themoving reaction mass. This is not a fluid shear. To obtain fluid shearit is essential to provide an agitation presently practiced in the art,propattern in a fiuid mass such that portions of the mass are infrictional, sliding contact with other portions of the mass. Fluid shearas used herein refers to this internal sliding frictional contactbetween like liquid masses as distinguished from external slidingfrictional contact between unlike masses i.e. vessel walls and reactionmass. The inevitable incident of shear is friction and this meansproduction of heat. A convenient index of the quality of shear or thedegree of friction being obtained is the amount of heat produced. It isto be emphasized that the preparation of the catalyst and the practiceof the method of this invention is no wise dependent upon some criticaltemperature being achieved in the reaction vessel. Rather the heatdifferential induced by shear agitation in the reaction vessel betweenthe start of the reaction and the end of reaction is What is importantin this invention. It has been found that the desirable catalystproducts described above are produced when the agitation in the reactionvessel is sufficient to give an output of 10 calories per minute perliter of agitated fluid. Calorie output is easily determined bymultiplying the heat rise obtained in the particular agitated fluid,e.g. the reaction solvent times the volume and times the specific heatthereof. Since the reaction to form the catalyst is exothermic, it isbest to ascertain prior to carrying out catalyst preparation whether aparticular vessel and agitating system will produce sufiicient shear,e.g. by agitating the proposed reaction solvent only. Then havingestablished that minimum shear at least is obtained in a particularvessel catalyst preparation can be carried out without constantmeasurement of shear development.

Alternatively quality and quantity of shear can be compared with a benchmark of a 5 C. rise at steady state over ambient temperature obtainedwhen agitating 500 milliliters of heptane in an insulated vessel undersubstantially adiabatic conditions.

As pointed out in the paragraph next above, fluid shear is essential tothe practice of the present method. Therefore the reactants, thetransition metal halide and the organo-aluminum compound, must both bein the fluid state. Thus their reaction can be ettected where thereactants are gaseous fluids or liquid fluids. Liquid fluidity ispreferred for convenience in handling the reactants and the product.Liquid fluidity is achieved by using normally liquid reactants (i.e. atroom temperature) or by dissolving normally solid reactants in asuitable inert organic solvent or mixture of solvents such as are wellknown in the art. The two reactants can be dissolved in the same ordifferent solvents. One reactant can be placed in the reaction vessel asa solution and the other can be in the undissolved but liquid state.

It is preferred to dissolve the reactants Whether they be liquids or notin an inert organic liquid selected from the class of aromatic andsaturated aliphatic hydrocarbons and halogenated aromatic hydrocarbonswhich are solvents for the reactants but which do not dissolve thereaction product. Specific classes of such solvents include saturatedaliphatic and alicyclic hydrocarbons such as alkanes and cycloalkanese.g. heptane and cyclohexane, aromatically unsaturated hydrocarbons,such as benzene, alkyl substituted aromatically unsaturated hydrocarbonssuch as toluene, and halogen substituted aromatically unsaturatedhydrocarbons, such as dichlorobenzene.

As the transition metal halide there can be used in this inventioncompounds having the formula MO X wherein M is a transition metalselected from groups IVb, V-b or Vlb of the Deming periodic table(Handbook of Chemistry and Physics, 30th ed., page 312) for example, Ti,Zr, Hf, V, Ni, Ta, Cr, M0, and W; and having a valence z greater than 3in the compound MO X O is oxygen and X is a halogen; b is an integerhaving a value of from 2 to z; and a is an integer equal to z-b/Z andhas a value of 0 or greater. Thus the term transition metal halide asused herein includes metal halides and metal oxyhalides. Particularlydesirable metal compounds in this invention are titanium, tetrachloride,vanadium oxychloride and chromium oxychloride.

T he above transition metal halides are reacted with an organo-aluminumcompound having the general formula m 3m wherein R is a hydrocarbon freeof aliphatic unsaturation such as alkyl e.g. ethyl, propyl, and butyl,or aryl e.g. phenyl; m is a number greater than zero and not more than3; and Y is a halogen group.

The proportions of the compound MO X and AlR Y are not narrowlycritical. As a minimum there should be used a sufficient amount of thealuminum compound to reduce the valence of a portion of the transitionmetal M to less than 3. it will be noted from the above-givendescription of the compound MO X the valence of M, termed there 2 wasgreater than 3 in the compound MO X Valence of M in any specificcompound will of course be an integer but it is contemplated in thisinvention that mixtures of more than one metal halide or mixtures ofmetal halides wherein the metal exists in different valence states inthe two compounds can be used provided the average valence for thetransition metal is greater than 3. Where there is but one metal halidepresent to react with the organo-aluminurn com pound the term z willequal 4 or more. Average valence of the transition metal in aparaticular reaction system can be calculated from the data provided byan analysis of the reaction system according to the method of E. G.Tabakova and Z. V. Soloveva, Zavodskaya Lab. 22, No. 12, 1417 (1956).

The quantity of aluminum compound necessary to reduce the valence stateof transition metal to less than 3 is in the first instance dependent onthe number of transition metal reactive groups i.e. hydrocarbon groupsbound to the aluminum. For that reason it is usual to consider thehydrocarbon equivalents of the aluminum com pound rather than moles ofaluminum compound in calculating proportions of catalyst reactants. Itis easily seen that triethyl aluminum has 3 hydrocarbon equivalents,diethyl aluminum monochloride 2 hydrocarbonequivalents and so forth.

In carrying out the method of this invention, it is essential to employan amount sufiicient to reduce the valence of a portion of the metal Mto less than 3. The

reaction of the hydrocarbon aluminum compound with the transition metalhalide proceeds by first reducing the valence of the transition metalfrom its valence in the compound MO X (z in the formula above) to 3.When the valence is at 3 the transition metal halide precipitates andthe reaction mixture becomes two phase. For the initial reaction to avalence of 3, there is used one hydrocarbon equivalent for each valenceabove 3. Thus, for

example, to reduce TiCL; to TiCl one hydrocarbon equivalent is added,reducing the valence of Ti from 4 to 3. Because the 3 valence statemetal compounds are solids and only a small percentage of the surface ofthe constituent particles is metal atoms and these metal atoms are onlya portion of the amount of M in the complex, only enough hydrocarbon toreact with and reduce these atoms to a valence less than 3 is needed.Thus as little as 1 percent excess of hydrocarbon equivalent over theamount used to reduce the valence of M to 3 may be sufficient to reduceall surface M atoms, i.e. all available M atoms, to a valence less than3. Therefore, to reduce a metal M having a valence of 4 to less than 3,as little as 1:01 hydrocarbon equivalents is sufficient. Similarly WhereM has a valence of 5, e.g. V in VOCl 2.01 hydrocarbon equivalents issuificient. And Where M has a valence of 6, e.g. Cr in C1O Cl 3.01hydrocarbon equivalents is suflicient. It is preferred to add a 50percent or greater excess, i.e. another one-half of a hydrocarbonequivalent to the amount necessary to reduce the valence of M to 3. Thusit is preferred to employ at least 1.5 hydrocarbon equivalents to reducetetravalent metals, at least 2.5 hydrocarbon equivalents to reducepentavalent metals and at least 3.5 hydrocarbon equivalents to reducehexavalent metals.

Another factor to be considered in choosing proportions of aluminumcompound to metal halide is the comparative activity of the aluminumcompound. For example the aluminum triallryis are more vigorousalkylating agents than the corresponding dialkyl aluminum monohalides,which in turn are more vigorous than the corresponding monoalkylaluminum dihalides.

Use of excessive amounts of aluminum compound results in overreductionof the transition metal, perhaps to the metal itself. In general, amaximum of 30 equivalents of hydrocarbon per equivalent (i.e. mole) ofmetal halide should be observed. Very careful reaction and closelycontrolled low temperatures are necessary to avoid overreduction whenusing greater than 30 equivalents of hydrocarbon per equivalent ofmetal. Where reaction temperature is above about 100 C. it is desirableto lower the number of hydrocarbon equivalents below 30 progressively astemperatures used rise above 100 C.

The catalyst components can be added to the reaction zone in any order.In continuous reaotion systems two independent streams one of each ofthe two components can be advantageously fed into one end of theagitatingreaoting zone. Rate of addition and contact times are notcritical with contact times ranging from, for ex ample, 30 seconds to 2hours having been successfully used. Portions of one or the other of thecatalyst components can be added to the'whole of the other catalystcomponent. i

Particularly when accomplishing high temperature reduction in preparingthe catalyst it is preferred to add only a little of the aluminumcompound and to add the remainder at a lower temperature.

The temperature at which the catalyst is prepared is not critical in themethod. of this invention. Generally speaking the reaction can beelfected at temperatures ranging from 0 C. to 200 C., and particularly25 to 175 C. but temperatures higher or lower can be employed withsuccess.

The use of pressure is not required, except to keep liquid a volatilereaction solvent at elevated reaction temperatures, and will notordinarily be used, since numerous organic solvents which are liquid atelevated temperatures are readily available.

In the practice of a preferred embodiment of themesent invention asolution of a lower alkyl aluminum compound e.g. tri-n-propyl ortriisobutyl aluminum in n-heptane orn-decane is added dropwise over thecourse of about an hour to an agitated solution of either titaniumtetrachloride or vanadium oxychloride in the same solvent until there isa molar ratio of aluminum trialkyl to transition metal halide of from0.5 :1 to 1021.0. Bulk temperature is permitted to rise uncontrolledduring this rst addition step. Concentration of the components in theirrespective solutions and the reaction mixture are in no way critical.Convenience in handling is the determining factor.

The solution is then further agitated in a suitable apparatus, that is,an apparatus demonstrated to be capable of imparting suificient motionto the reaction solution that the resulting fluid turbulent shearproduces heat at a pre: ferred rate of at least 100 calories per minuteper liter of solvent. Preferred devices include a Duplex Dispersatorespecially in a baffled vessel, a Tri-Homo Disc Mill and a Colloid Mill.Agitation with high shear is continued for about an hour. Additionalaluminum alkyl is then added. The reaction solution is cooled to below60 C. if necessary, prior to the further addition of aluminum trialkylto avoid excessive reduction of the transition metal halide. The secondaddition of aluminum trialkyl brings the total molar ratio of aluminumtrialkyl to transition metal halide to 1.0210 to 11.0:1.0. The catalystsuspension thereby produced is removed under an inert atmosphere.

Catalyst prepared in accordance with the method of this invention aresuperior catalysts for the polymerization of olefinically unsaturatedhydrocarbons heretofore polymerized with Ziegler catalysts especiallythose which have the general formula wherein R is hydrogen, a saturatedaliphatic, alicyclic or an aromatic radical, alone or in mixture withone another.

The practice of the present invention is illustrated by.

EXAMPLE 1 ASTM grade n-heptane was dried with nitrogen until theeiiluent nitrogen contained less than 32 parts per million of Water. Toa 632.3 gram portion of the n-heptane there was added 9 milliliters of a0.1 M solution of triisobutyl aluminum in n-heptane and 35.30 grams ofCl. grade titanium tetrachloride and the solution blown under drynitrogen into a dried 2-liter baflled resin kettle. The kettle wasfitted with a 3" Duplex Dispersator, a dropping funnel thermometer,nitrogen source, and. reilux condenser. The Dispersator was driven at2000 rpm. and a solution of 58.98 grams of triisobutyl aluminum in 1596grams of n-heptane was added dropwise over a period of 142 minutes. Thetemperature rose from 26 C. to 49 C. during this period. The slurry wasagitated an additional 24 minutes at 4950 C. The resulting dark brownsuspension was removed in vacuo in an atmosphere of nitrogen. Thesuspension weighed 96l.9 grams, had a density of 0.739 gram/ml. and anominal triisobutyl aluminum to titanium tetrachloride ratio of 1.75:1.

EXAMPLE 2 Pure n-decane was washed with sulfuric acid and fractionatedand then dried with nitrogen until the efiluent nitrogen contained lessthan 15 parts per million of water. To a 356 gram portion of then-decane there was added 3.6 grams of 0.1 M solution of triisobutylaluminum in n-decane and 38.14 grams (200 millimoles) of CF. gradetitanium tetrachloride. The solution was transferred under dry nitrogenpressure to a dried l-liter bafiled resin kettle fitted as the 2-literkettle in Example 1. The Dispersator was driven at 2000 r.p.m. and asolution of 19.89 grams (100 millimoles) distilled triisobutyl aluminumin 74.5 grams of n-decane was added dropwise over a period of 45minutes. The temperature rose from 25 C. to 50 C. during this period.The resulting dark brown suspension was agitated an additional 65minutes at between 5055 C. and then heated with continuing agitation toatmospheric reflux C.). After 40 minutes at 170 C. the brown suspensionhad turned completely purple. Agitation was continued at 2000 r.p.m. andthen kept at 170 C. for another 30 minutes. The reaction mixture wasthen allowed to cool to less than 60 C. over the course of 50 minutes.The obtained purple suspension was treated with an additional 19.89grams of distilled triisobutyl aluminum dissolved in 72.7 grams ofn-decane. This addition was accomplished over a period of 19 minutes.During this period the temperature of the catalyst mixture dropped to 51C. Agitation sufiicient to maintain the mixture at 47-50 C. wascontinued for70 minutes. The

7 catalyst was removed in vacuo in an atmosphere of dry nitrogen. Theproduct was a catalyst suspension weighing 548 grams, having a densityof 0.765 gram/ml. and containing 0.108 gram of TiCl and A1(i-Bu)reaction product per milliliter.

EXAMPLE 3 A solution of 37.69 grams (197 millimoles) of Cl. gradetitanium tetrachloride in 365.2 grams of n-decane which had beenpurified and dried as in Example 2 was heated to reflux in a l-literbafiled flask equipped as in the previous examples. The Dispersator wasdriven at 2000 rpm. and, as soon as the solution began refluxingdropwise addition of a solution of 24.94 grams (149 millimoles) oftri-n-propyl aluminum (93.6% pure) in 72.1 grams of dry n-decane wasbegun. The addition took 45 minutes. The temperature of the reactionsolution rose to 172 C. The resulting purple-grey suspension waspermitted to cool slowly to 42 C. with agitation at 2000 rpm.continuing. Thereupon 47.74 grams (285 millimoles) of the tri-n-propylaluminum dissolved in 72.7 grams oi dry n-decane was added over thecourse of 23 minutes while the reaction mixture temperature was between41 and 42 C. Agitation was continued for another 20 minutes and theresulting catalyst slurry removed in vacuo under nitrogen. There wasobtained 594.4 grams of catalyst slurry having a density of 0.760 gram/ml. and containing a total of 0.141 gram of TiCl and Al(i-Pr) reactionproduct per milliliter.

EXAMPLE 4 ASTM grade n-heptane was dried with nitrogen until theefiluent nitrogen contained less than 30 parts per million of water. Toa 450 milliliter portion of this n-heptane there was added 4.5milliliters of 0.1 M triisobutyl aluminum in n-heptane and, after 15minutes, 7.6 grams (0.0438 mole) technical grade vanadium oxychloride.The solution was pressure transferred to a 1-liter kettle equipped as inthe previous examples, except that a 1 /2 inch Duplex Dispersator wasused in place of the 3 inch device used in the previous examples.Agitation was provided by rotating the Dispersator at 2000 r.p.rn. Asolution of 17.7 grams (0.0894 mole) of distilled triisobutyl aluminumin 100 milliliters of dry n-heptane was added dropwise in two equalportions. The first portion of the triisobutyl aluminum was added over aperiod of 18 minutes. Temperature of the reaction mass increased from 26C. to 36 C. The solution was agitated for an additional hour at 36 C.and then the second portion of the triisobutyl aluminum was added alsoover a period of 18 minutes and at 27-29 C. The resultant dull violetsuspension was agitated for a half hour and then removed to glassbottles in vacuo and under nitrogen. The yield of catalyst suspensionwas 399.5 grams. The density was 0.779 gram/rnL, corresponding to a 0.26millimole/ml. total catalyst component concentration at a nominalAl(i-Bu) VOCl ratio of 2.0: 1.

EXAMPLE n-Heptane was dried as in Example 4 to a nitrogen effluent watercontent of less than 40 parts per million. To 450 milliliters of thisn-heptane there was added 5 milliliters of 0.1 M triisobutyl aluminumand 7.4 grams (0.0426 mole) technical grade vanadium oxychloride. Thesolution was transferred with nitrogen pressure to a 1-liter bafl'ledflask equipped as in the previous examples, and with the 3 inch DuplexDispersator. Agitation was at 2000 r.p.m. Distilled triisobutylaluminum, 25.8 grams (0.130 mole) in 100 milliliters of dry n-heptane,was added dropwise over a period of 65 minutes at temperatures of from29 to 39 C. A dull violet suspension was obtained and this was removedin vacuo under nitrogen and stored protected in a glass vessel. Thesuspension weighed 396.5 grams and had a density of 0.697 gr-am/milliliter which corresponds to 0.303 millimole total cat- A e 'alystper milliliter at a nominal ratio of Al(i-Bu) :VOCl of 3:1.

EXAMPLE 6 A one-gallon stainless steel autoclave equipped with an anchortype agitator and the conventional auxiliary openings andinstrumentation was charged with 2 liters of dry pure xylene and purgedwith dry nitrogen until the effiuent nitrogen stream contained less than15 ppm. of water. To this was added 12.5 milliliters of the catalystsuspension prepared in Example 3, providing a total of 1.76 grams ofactive catalyst. to 125 C. within 40 minutes under a blanket ofnitrogen, purged free of nitrogen, and pressured with propylene to apartial pressure of p.s.i. A drop in monomer pressure indicated thatpolymerization commenced immediately. Propylene was fed on demand at C.and 100 p.s.i. partial pressure for six hours. The monorner feed wasthen stopped and the autoclave permitted to cool. The autoclave contentswere quenched with five gallons of isopropanol by expelling theautoclave contents under nitrogen pressure into the isopropanol. Thepolypropylene polymer was shredded by vigorous agitation and filtered.The resultant white polymer, after drying to constant weight, weighed443 grams, equivalent to a catalyst productivity of 250 grams of polymerper gram of total catalyst components. The polymer was highlycrystalline, melted at 167168 C. and was 88% insoluble in boilingdiethyl ether.

EXAMPLE 7 To a three-liter glass resin kettle equipped with an agitator,a thermometer, condenser, nitrogen source and inlet for gaseous monomer,was added 1,200 milliliters ASTM grade n-heptane. The n-heptane wasdried by purging with dry nitrogen until the efiluent moisture levelfell below-50 ppm. To this was added 6 ml. containing a total 'of 1.73grams of catalyst components of a brown catalyst slurry prepared in amanner of Example 1, but at a mole ratio of A1(iBu) /TiCl of 1.5:1. Amixture of dry ethylene and propylene, containing 10% propylene byweight, was passed through the n-heptane at 2.5 liter per minute atatmospheric pressures. The exothermic heat of reaction raised thereaction temperature from 25 to 69 C. and maintained it at 69 C. for sixhours. After this time, the reaction mass was too viscous to stir, andthe monomer feed was shut off; The reaction mass was quenched with oneliter of methanol and filtered. After drying there was obtained 186grams of a white, ethylene-propylene copolymer equivalent to a catalystproductivity of 108 grams of copolymer per gram of catalyst.

EXAMPLE 8 To a three-necked flask equipped with a dropping funnel,condenser, stirrer, thermometer and source of dry nitrogen was added 100milliliters of pure dry toluene and 100 milliliters pure dry styrene. Tothis mixture was added 3.8 milliliters of catalyst suspension preparedaccording to Example 2 plus an additional 0.198 gram dis tilled Al(i-Bu)resulting in a total of 0.58 gram of catalyst components. Thepolymerization was permitted to continue for one hour at 75-77 C. Thenthe reaction was quenched with isopropanol and the polymer filtered. Theresultant polymer was washed with methanol and dried in vacuo at 6570 C.to constant weight. There was obtained per gram total catalyst 60.4grams crystalline polystyrene which was 93.3% insoluble in boilingmethyl ethyl ketone.

EXAMPLE 9 A No. 4 Tri-Homo rotating cone mill with a No. 1 rotor coneand a No. 1 stator cone was utilized at a clearance of 0.0005.Triisobutyl aluminum (10% by weight solution in dry iso-octane) andtitanium tetrachloride (10% by weight solution in dry iso-octane) werefed from agi The autoclave was heated tated, stainless steel tanksthrough stainless steel pumps to the mill suction and from the milldischarge to an agitated stainless steei receiver. The rate of flow ofthe respective solutions was controlled to provide an overall ratio 10temperature of the agitated slurry rising to 50 C. The reaction mixturewas heated to reflux at 162 C. Within 35 minutes, 15 minutes later at 171.5 (1., the suspension was completely purple. The suspension was heatedunder of 0.75 :1 mole Al(i-Bu) :TiCl It was necessary to cool 5 reflux35 minutes longer, and cooled Within 80 minutes the mill to maintain thebulk temperature of the system to 47 C. At this point 89.31 gramsdiethyl aluminum below 50 (3. A typical analysis for a catalyst slurrychloride (:740 millimoles) dissolved in 71.77 grams of made in thismanner, indicates no tetravalent titanium, pure dry n-decane was addedwithin 15 minutes at 47-48 9.2% trivalent titanium, and 8% divalenttitanium; accord- C. Agitation was continued two hours longer, withouting to the method of E. G. Tabakova and Z. V. Soloveva, 10 any externalheat, at 51-55 C. The reaction tempera- Zavodsk-aya Lab, 22, No. 12,1417 (1956). This catalyst ture was kept above the ambient temperatureof 23 C. slurry was then stored protected from atmospheric conby theenergy imparted to the suspension by high shear tamination. agitation.The catalyst slurry was then removed in vacuo Ethylene polymerizationwas carried outwith this cataunder nitrogen. The final slurry weighed668.47 grams, lyst using a battled autoclave equipped with an agitatordensity 0.79 g./ml., corresponding to 0. 295 milliequivaand thenecessary piping to feed continuously ethylene, lent of Ti/mL, at anoverall molar ratio of diethyl alumihydrogen, catalyst slurry andheptane, and also to remove num chloride to titanium tetrachloride of3.56: 1. a polymer solution continuously. Provision was made for EXAMPLE23 occasional venting or sampling of tne vapor space above thepolymerization. At .a temperature of 130 C. and a Reagent-grade xylene(B.P.R. 137-140 C.) is dried pressure of 130-145 psi. gauge, therewasfed to the With nitrogen until the efliuent nitrogen contains less thanautoclave the heptane slurry of the above catalyst at a 0 ppm. Water. Toa 657.3 gram porti n Offh y rate of 2-4 lbs/hr. together with anadditional amount xylene there is added 18.93 grams C.P. grade T101 andof triisobutyl aluminum in heptane, again at 24 lb./.-hr. the t n blOWIllllldfir Hitmgfll a f 541m in an amount ulficient to bring the overall mla atio 25 baffled resin kettlefitted as the Z-liter kettle inExample 1. or" Al/Ti to 1.5:1 in the polymerization vessel. Ethylene The3" Duplex Dispersator is driven at 2,000 lip-m and gas and hydrogen wereadded to a total pressure of 130- a solution of 27.31 gramsrecrystallized triphenyl alu- 145 p.s.i. Heptane was added at 90-120lbs/hr. with a mlmlm in 2,142 grams dry, hot xylene is added dropwisetotal concentration of catalyst of 1.9 millimoles per liter, Within 83minutes- The temperature Iise q 23 to a contact time in the autoclave of2-3 hours, and with The resflltlng brown 81151161181011 1S agitated an7-9% hydrogen in the vapor space, there was produced additional 126minutes at between 50-55 C. The brown during the 12-hour run, apolyethylene of 0,9618 d it suspension is removed in vacuo in anatmosphere of nitroat an overall productivity of 175 lbs. of polymer perIt Welghs Elb0112,68 7 grams, has a density of -7 pound of tot l tal t,g./ml., and a nominal triphenyl aluminum to titanium tetrachloride ratioof 1.05:1. EXAMPLES 1041 What is claimed is:

A series of polymerizations of various monomers and 1. Method for thepreparation of highly geometrically mixtures of monomers were carriedout in the equipment uniform, essentially spheroidal particulateorganic-metallic and in the manner of Examples 1-5 using catalystsprecatalysts from pared as in Example 9 using various alkyl aluminumcom- (A) transition metal halides having the formula pounds differentratios of catalyst components and dif- MO Y ferent temperatures forcatalyst preparation. To demonb strate the resistance of these catalystslurries to aging dewherein M is a transition metal selected from theterioration the various catalysts were aged under nitroclass consistingof metals of groups lVb, Vb and gen at about 25 C. for periods rangingfrom 1 to 167 V11) of the Deming periodic table having a valence 2 days.greater than 3 in the compound MO Xa; O is oxygen Table II Organo-Transition Highest Catalyst age, aluminum metal Moles catalyst days 25Polymer and yield (gram/gram compound compound Al/moles Ti preparation0. under N2 catalyst) temperature Al(i-Bu) 1.5 45 38 145ethylene/propylene copolymer. Aid-Bu); 2.25 170 20 307 polypropylene.Al(i-Bu) 1.0 170 2 527 polypropylene. 1.5 170 l 263 polypropylene. 2 4520 113 ethylene/propylene copolymer. 1. 5 44 14 108 ethylene/propylenecopolymer. 2.25 170 28 492 polypropylene. 2.25 170 120 178polypropylene. 1.5 170 167 42 polypropylene. 1.5 170 8 polystyrene.Al(i-Bu)3 2 47 15 12 polyethylene.

1116-1311); 1.5 50 19 175 polyethylene.

l Gram polymer/gram catalyst/hour. mean triisobutyl aluminum,

EXAMPLE 22 tated an additional 35 minutes, with no external heat, the

The symbols Al(i-Bu) Al(Pr)a and Al(Et) in Table II and throughout thespecification tri-n-propyl aluminum and triethyl aluminum respectively.

and X is ahalogen; b is an integer having a value of 2 to z and a is aninteger equal to z-b/Z and has a value of at least zero, and

(B) an organo-aluminum compound having the formula wherein R is ahydrocarbon group free of aliphatic unsaturation, m is a number greaterthan Zero and not more than 3, and Y is a halogen, which comprisescontacting said metal halide reactant with a suflicient amount of saidorgano-alurninurn compound awaeaa 2. Method for the preparation ofhighly geometrically uniform essentially spheroidal particulateorgano-metallic (B) an organo-alurninum compound having the formula AlRY wherein R is a hydrocarbon group free of aliphatic unsaturation, m isa number greater than zero and l2 oxygen and X is a halogen; b is aninteger having a value of 2 to z and a is an integer equal to z-b/Z andhas a value of at least zero, and (B) an organo-aluminum compound havingthe formula AlR Y wherein R is a hydrocarbon group free of aliphaticunsaturation, m is a number greater than zero and not more than 3, and Yis a halogen, which comcatalysts from rises contacti'r sa'd metal halidereactant with a (A) transition metal halides having the formulaSufficient i Said organo aluminum Mo X pound reactant to reduce thevalence of a portion wherein M is a transition metal selected from theif 2;gf f igg i l if,231,iig ii infn igiiiiii g s g g s g g of gi sg ffig fig g l g solvent therefor which is not a solvent for theirgrfiatfir than compound O reaction product, and throughout thecontacting Gen and X is a halogcn. b is an integerahagling a valup stepsubjecting the reactants to continual high speed gfpz to z and a isinteger equal to Z b/2 agitation in a pattern characterized by internalfluid has avalue of at East Zero, and shear whlch 1s sufficrent toproduce at least 100 calories per minute per liter of solvent andprecipitating the reaction product from the reaction medium.

5. Method for the preparation of highly geometrically uniform,essentially spheroidal particulate organo-rnetal- 2 not more than 3, andY is a halogen, which com- 5 11c catalysts prises contacting said metalhalide reactant with a (A) transmon metal halides havmg the formulasufficient amount of said organo-aluminum compound MO X reactant toreduce the valence of a portion of M to h 1 h less than3while bothreactants are fluid, and throughi 6mm a transltlon metal Se ected from te out the contacting step subjecting the reactants to Cass conslstmg iof groups 1vb Vb and continual high speed agitation in a pattern charac-VIb of the D m penodlc table having a Yalence z tcrized by internalfluid shear which is sufficient to greater :[han 3 m thfi MOaXb; 1sOxyggn produce at least 100 calories per minute per liter and X 15 ahalogfm; b an Integer hawng a value of agitated of 2 to z and a 1s aninteger equal to zb/2 and 3. Method for the preparation of highlygeometrically has a value of at kiast Zero and uniform, essentiallyspheroidal particulate organo-metallic (B) an organo'alummum compoundhaving the catalysts from mula (A) transition metal halides having theformula A1RmY3m MOaXh 40 wherein R is a hydrocarbon group free ofaliphatic unsaturation, m is a number reater than zero and wherein M isa transition metal selected from the not more h 3 and y is aghalogen,which f t h g m f gl t g llz Vb 1 VIb prises contacting said metalhalide reactant with 0 6 61111112; Pfiflo a e avmg 3 Va @1166 Z anamount of said or ano-aluminum corn ound greater'than 3 in the Q P 0 1 0is oxygen reactant sufiicient to pr vide a number of li ydrm and X 15 al 15 an Integer having a Value of carbon equivalents equal at least tothe difference 2 l Z i t l 13 t Images equal to 2 and has a between 3and the valence z of M in the compound Va 0 a eas an M0 X plus anadditional one percent thereof by (B) an organo-alurrunum compoundhaving the formula Weight and not more than 30 hydrocarbon equiva A1R Ylents while each reactant is dissolved in a reaction wherein R is a hdrocarbon rou free of ali hatic medium-n c9mpnsmg an Inert sO-lventthereunsaturation m a numberg Pager than and for which is not a solventfor their reaction product, not more than 3 and Y is a halogen whichcomand throughout tile ngilctmg Step suPia-(yangthe prises contactingsaid metal halide reactant with a gi f i'g i g z gg ii z igi g i ggsf jgg 223:?5: 23: 2: ig:gifg i g g ggag fi fi ig is sufiicient to produce atleast 10 calories per minless than 3 while each reactant is dissolved ina reper g and-preclplt-atmgi the reaction medium comprising an inertorganic solvent 6 sggfi g g s fi g g g g gg 52 1;? ggk g if 2 3 1S 2?thfitlr gi 6 uniform, essentially spheroidal particulateorgano-metaliii; th e ri zictan tg li d dntinii'il lii h ggeicl alii' n0 lie catalysts from r g c in a pattern characterized by internal fluidshear (A) transltlon metal hahdes havmg the formula which is sufficientto produce at least 10 calories per a b fig gigg i g fi igii ggg ii gsfi the 6 wherein M is a transition metal selected from the classconsisting of metals of groups IVb, Vb and 4. Method for the preparationof highly geometrically uniform, essentially spheroidal particulateorgano-metallic catalysts from i (A) transition metal halides having theformula Mopc wherein M is a transition metal selected from the classconsisting of metals of groups lVb, Vb and Vlb of the Deming periodictable having a valence z greater than 3 in the compound MO X O is VIb ofthe Deming periodic table having a valence z greater than 3 in thecompound MO X O is oxygen and X is a halogen; b is an integer having avalue of 2 to z and a is an integer equal to zb/2 and has a value of atleast zero, and (B) an organo-alurninum compound having the formula AlRY wherein R is a hydrocarbon group free of aliphatic l3 unsaturation, mis a number greater than zero and not more than 3, and Y is a halogen,which comprises contacting said metal halide reactant with an amount ofsaid organo-aluminum compound reactant suflicient to provide a number ofhydro 5 carbon equivalents equal at least to the difference between 3and the valence z of M in the compound M0,,X plus an additional 50percent thereof by weight and not more than 30 hydrocarbon equivalentswhile each reactant is dissolved in a reaction medium comprising aninert organic solvent therefor which is not a solvent for their reactionproduct, and throughout the contacting step subjecting the reactants tocontinual high speed agitation in a pattern characterized by internalfluid shear which is sufficient to produce at least 100 calories perminute per liter of solvent and precipitating the reaction product fromthe reaction medium.

7. Method claimed in claim 6 wherein the transition metal halide istitanium tetrachloride, the organo-aluminum compound is triisobutylaluminum and the reaction medium is n-heptane.

8. Method claimed in claim 6 wherein the transition metal halide istitanium tetrachloride, the organo-aluminum compound is tri-n-propylaluminum and the reaction medium is n-heptane.

9. Method claimed in claim 6 wherein the transition metal halide istitanium tetrachloride, the organo-aluminum compound is triethylaluminum and the reaction medium is n-heptane.

10. Method claimed in claim 6 wherein the transition metal halide isvanadium oxychloride, the organo-aluminum compound is triisobutylaluminum and the reaction medium is n-heptane.

11. A highly geometrically uniform essentially spheroidal particulate,rounded organo-metallic catalyst which is resistant to agglomeration andfree of sharp edges and irregular contours and which has an averageparticle size diameter between 200 and 300 angstroms and no appreciablenumber of particles exceeding 500 angstroms, said catalyst being thereaction product of (A) a transition metal halide having the formula MOX wherein M is a transition metal selected from the class consisting ofmetals of groups No, Vb and Vlb of the Deming periodic table having avalence z greater than 3 in the compound MO X O is oxygen and X is ahalogen; b is an integer having a value of 2 to z and a is an integerequal to z-b/Z and has a value of at least zero, and

(B) an organo-aluminum compound having the formula wherein R is ahydrocarbon group free of aliphatic unsaturation, m is a number greaterthan zero and not more than 3, and Y is a halogen,

21. The organo metallic catalyst claimed in claim 21 wherein thetransition metal halide is titanium tetrachloride. 1

References @ited by the Examiner UNITED STATES PATENTS 2,491,116 12/49Kraus et a1. 252-429 2,647,111 7/53 Shusman 260-935 2,659,717 11/53 Park260-935 2,962,451 11/60 Schreyer 252-429 2,976,252 3/61 Leary et al.252-429 2,991,157 7/61 Orzechowski et al. 252-429 3,041,325 6/62 Franham252-429. 3,058,970 10/62 Ruse et al 252-429 5o 14 the reaction of (A)and (B) being conducted while in a fluid phase and under continual highspeed agitation in a pattern characterized by internal fluid shearsufiicient to produce at least 10 calories per minute per liter ofagitated fiuid.

12. The organo-metallic catalyst claimed in claim 11 wherein thetransition metal halide is titanium tetrachloride and theorgano-aluminum compound is triisobutyl aluminum.

13. The organo-metallic catalyst claimed in claim 11 wherein thetransition metal halide is vanadium oxychloride and the organo-aluminumcompound is triisobutyl aluminum.

14. Method for the preparation of purple crystalline catalyst suspensionof the reaction product of titanium tetrachloride and triisobutylaluminum from brown amorphoussuspensions thereof which comprises heatingthe brown amorphous suspension to a temperature greater than thetemperature of formation and throughout the heating step subjecting thesuspension to continual high speed agitation in a pattern characterizedby internal fluid shear which is suflicient to produce at least caloriesper minute per liter of suspension.

15. Method claimed in claim 6 wherein the organoaluminum compound is adiallryl aluminum halide.

16. Method claimed in claim 15 wherein the dialkyl aluminum halide isdiethyl aluminum chloride.

17. The organo metallic catalyst claimed in claim 11 wherein thetransition metal halide is titanium tetrachloride.

18. The organo metallic catalyst claimed in claim 11 wherein thetransition metal halide is vanadium oxychloride.

19. The organo metallic catalyst claimed in claim 11 wherein the organoaluminum compound is a dialkyl aluminum halide.

20. The organo metallic catalyst claimed in claim 21 wherein the dialkylaluminum halide is diethyl aluminum chloride.

r TOBIAS E. LEVOW, Primary Examiner.

PHILIP E. MANGAN, SAMUEL H. BLECH,

Examiners.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,179,604 April 20, 1965 Arthur K. lngberman It is hereby certified thaterror appears in the above numbered patent requiring correction and thatthe said Letters Patent should read as corrected below.

Column 14, lines 37 and 40, for the claim reference numeral "21", eachoccurrence, read. 1s

Signed and sealed this 18th day of January 1966.

( L) Attest:

ERNEST W. SWIDER Attesting Officer EDWARD J. BRENNER Commissioner ofPatents

1. METHOD FOR THE PREPARATION OF HIGHLY GEOMETRICALLY UNIFORM,ESSENTIALLY SPHEROIDAL PARTICULATE ORGANO-METALLIC CATALYSTS FROM (A)TRANSITION METAL HALIDES HAVING THE FORMULA